CN114914413B - Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery - Google Patents
Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery Download PDFInfo
- Publication number
- CN114914413B CN114914413B CN202210440489.9A CN202210440489A CN114914413B CN 114914413 B CN114914413 B CN 114914413B CN 202210440489 A CN202210440489 A CN 202210440489A CN 114914413 B CN114914413 B CN 114914413B
- Authority
- CN
- China
- Prior art keywords
- carbon
- sodium
- ferrous
- coated
- fluorophosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 100
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000011734 sodium Substances 0.000 title claims abstract description 66
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 60
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title claims description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- BFDWBSRJQZPEEB-UHFFFAOYSA-L sodium fluorophosphate Chemical compound [Na+].[Na+].[O-]P([O-])(F)=O BFDWBSRJQZPEEB-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000007921 spray Substances 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- -1 organic acid salt Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012855 volatile organic compound Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 9
- 239000012071 phase Substances 0.000 description 16
- 239000000725 suspension Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly discloses a preparation method of a carbon-coated ferrous sodium fluorophosphate material, which comprises the steps of carrying out spray drying-roasting treatment or spray pyrolysis treatment on raw material slurry containing an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source to obtain carbon composite precursor particles; and then placing the precursor particles in an atmosphere containing volatile organic matters and carrying out gas phase carbon deposition treatment at the temperature of 200-350 ℃ to prepare the carbon-coated ferrous sodium fluorophosphate material. The invention also comprises the material prepared by the preparation method and the application of the material in sodium ion batteries. The preparation method can effectively solve the problems of heterogeneous phase, nonuniform carbon coating structure, unsatisfactory conductivity and the like in the preparation process of the ferrous sodium fluorophosphate, and can effectively improve the electrochemical performance of the ferrous sodium fluorophosphate.
Description
Technical field:
the invention belongs to the technical field of sodium ion battery materials, and particularly relates to the technical field of sodium ion battery anode active materials.
The background technology is as follows:
lithium ion batteries have been widely used in portable electronic products because of their high energy density, long cycle life, and other advantages. With the development of society, the demand for energy storage Fa is strong. However, limited lithium resources limit the further development of lithium ion batteries, and the development of suitable energy storage systems is highly desirable. The abundant sodium resources and similar reaction mechanisms to lithium ion batteries have made sodium ion batteries prominent, with iron-based phosphates being the most widely studied.
Na 2 FePO 4 The crystal structure of the F material shows a layered structure, and is dioctahedral [ Fe 2 O 7 F 2 ]The units are formed by coplanar FeO 4 F 2 Regular octahedron is formed by connecting F atoms into a chain shape and is connected with PO 4 Tetrahedral connections form layers with two-dimensional ion channels that are easily diffused. Layered Na 2 FePO 4 F has higher theoretical specific capacity (124 mAh g -1 ) And a stable charge-discharge platform (3.0V), and extremely small volume change (< 4%), and is a sodium ion battery anode material with great commercialization prospect. But Na is 2 FePO 4 F has low electron and ion conductivities, and these inherent disadvantages limit Na 2 FePO 4 F further commercial development.
At present, the traditional modification method is to carry out carbon coating on sodium ferrous fluorophosphate, and comprises the steps of forming a carbon coating layer by utilizing pyrolysis of an organic carbon source at high temperature, and directly adding an inorganic carbon source for mixing for carbon compounding. In the two composite coatings, the organic carbon source is uniformly coated, but the graphitization degree of the carbon material is low and the electronic conductivity is low due to low reaction temperature, and the inorganic carbon source is difficult to uniformly coat, so that both coatings have certain limitations. In summary, at present, the composite of an organic carbon source and an inorganic carbon source is difficult to realize the preparation of a uniform carbon-coated coating layer at a low temperature, the electrochemical performance of the material is further required to be improved, and the commercialization is difficult.
The invention comprises the following steps:
to solve the problem of sodium ferrous fluorophosphate (Na 2 FePO 4 F) The first aim of the invention is to provide a preparation method of carbon-coated sodium ferrous fluorophosphate material, which aims at solving the problems of easy occurrence of mixed phase, low conductivity, non-ideal carbon coating effect and the like in the preparation processUnder the mild precondition, the problem that the sodium ferrous fluorophosphate is easy to generate hetero-phase is solved, the carbon coating structure and the electronic and sodium ion conductivity are improved, and the electrochemical performance of the sodium ion battery is improved.
The second object of the invention is to provide the carbon-coated ferrous sodium fluorophosphate material prepared by the preparation method and the application thereof in sodium ion batteries.
A third object of the present invention is to provide a sodium ion battery comprising the carbon-coated ferrous sodium fluorophosphate material and components thereof.
Different from other phosphate materials, the preparation process of the sodium ferrous fluorophosphate is easy to generate a hetero-phase, the ionic and electronic conductivity is not ideal, and the conductivity of the sodium ferrous fluorophosphate can be improved to a certain extent by carrying out carbon coating on the sodium ferrous fluorophosphate, however, the traditional carbon coating means generally needs more strict conditions, so that the hetero-phase generation of the sodium ferrous fluorophosphate can be further aggravated, the crystal structure is influenced, and the improvement of the overall performance is not facilitated. Aiming at the problems of difficult consideration of carbon coating morphology, conductivity and product phase purity and non-ideal electrochemical performance existing in the ferrous sodium fluorophosphate carbon coating process, the invention provides the following preparation method:
the preparation method of the carbon-coated ferrous sodium fluorophosphate material comprises the steps of carrying out spray drying-roasting treatment or spray pyrolysis treatment on raw material slurry containing an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source to obtain carbon composite precursor particles; the roasting temperature is 550-650 ℃; the temperature of spray pyrolysis is 550-650 ℃;
and then placing the precursor particles in an atmosphere containing volatile organic matters and carrying out gas phase carbon deposition treatment at the temperature of 200-350 ℃ to prepare the carbon-coated ferrous sodium fluorophosphate material.
According to the invention, the raw materials and the organic carbon source are subjected to spray drying-roasting treatment or spray pyrolysis treatment in advance, and then the subsequent vapor deposition treatment is matched, so that the synergy can be realized unexpectedly, the phase purity and the crystal structure of the sodium ferrous fluorophosphate can be effectively controlled under mild conditions, the composite morphology of the carbon material can be effectively improved, the graphitization degree is improved, the conductive network from inside to outside of the sodium ferrous fluorophosphate and the carbon material is improved, and the electrochemical performance of the prepared material can be synergistically improved, and in particular, the electrochemical performance of the prepared material under high multiplying power can be remarkably improved.
In the invention, the iron source is at least one of ferrous and/or ferric ion phosphate and organic acid salt; preferably at least one of ferric phosphate, ferrous oxalate dihydrate;
preferably, the phosphorus source is at least one of phosphoric acid, ammonium phosphate, monoammonium phosphate, diammonium phosphate, disodium phosphate, sodium dihydrogen phosphate, and ferric phosphate;
preferably, the fluorine source is at least one of sodium fluoride and ammonium fluoride;
preferably, the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium organic acid salts, sodium oxide and sodium hydroxide;
preferably, the organic carbon source is a water-soluble organic matter, and further preferably at least one of glucose, citric acid, starch, ascorbic acid, cyclodextrin and polyethylene glycol;
preferably, the solvent in the feedstock slurry comprises water; other water-soluble organic solvents are also permissible; the solvent is preferably water in view of the cost of treatment.
Preferably, in the raw material slurry, na: fe: p: f has an element mole ratio of 1.9-2.1: 0.9 to 1.1:1:1, a step of; further, the ratio may be stoichiometric.
Preferably, the weight ratio of the organic carbon source to the iron source is 1:1 to 10; further preferably 1:2 to 4.
In the invention, the solid particle size D50 in the raw material slurry is less than or equal to 300nm;
in the invention, the solid content in the raw material slurry is 30-60 wt.%;
preferably, the raw material slurry is obtained by pulping the raw materials and then performing ball milling and sand milling.
In the invention, the raw material slurry can be subjected to spray drying and then roasting treatment, so that the sodium ferrous fluorophosphate/C precursor material can be obtained.
In the invention, the inlet temperature of the spray drying process is 180-270 ℃, and more preferably 200-240 ℃; the spraying rate is preferably 20 to 40ml/min.
Preferably, the roasting atmosphere is a protective atmosphere;
preferably, the roasting temperature is 550-600 ℃, preferably, the heat preservation time is 4-16 h, preferably, 10-15 h;
in another embodiment of the invention, the precursor material is prepared by spray pyrolysis of the feedstock slurry.
Preferably, the spray pyrolysis temperature is 550-600 ℃; the spraying rate is preferably 20 to 40ml/min. According to the invention, the spray pyrolysis process is adopted, and the condition control is matched, so that the spray pyrolysis process can be further cooperated with the subsequent vapor deposition carbon process unexpectedly, the impurity phase of sodium ferrous fluorophosphate can be controlled more favorably, the carbon composite morphology and graphitization degree can be improved, and the electrochemical performance of the prepared material can be improved more favorably.
According to the invention, under the condition that the organic carbon source participates in the spray drying-roasting or spray pyrolysis process, the subsequent gas phase carbon deposition process is further innovatively combined, so that a synergistic effect can be brought to the aspects of heterogeneous phase control of the ferrous sodium fluorophosphate material, the composite mode of the carbon material, the graphitization degree and the performance of the sodium ion battery. The research of the invention also discovers that the temperature and the components of the volatile gas source in the treatment process can be further controlled, so that the synergy can be further improved, and the pure phase, the carbon composite morphology and morphology of the prepared material and the electrochemical performance of the material can be further improved.
The volatile organic matters are organic matters which are in a gaseous state at the temperature of 200-350 ℃;
preferably, the volatile organic compound is C 1 ～C 6 Alkane, C 2 ～C 6 Olefins, C 2 ～C 6 Alkyne, C 4 ～C 10 At least one of the ethers of (a).
The C is 1 ～C 6 Is C 1 ～C 6 Straight-chain or branched alkyl radicals of (2) may be, for example, methane, ethane, propaneAt least one of isopropyl alcohol; the C is 2 ～C 6 The olefin of (2) is a mono-or diene of the carbon number, and may be at least one of ethylene, propylene, and the like, for example. The C is 2 ～C 6 The alkyne (a) may be at least one of acetylene, propyne and the like. The C is 4 ～C 6 The ethers of (2) are preferably symmetrical or asymmetrical ethers, for example diethyl ether, butyl ether.
Further preferably, the volatile organic compound comprises C 2 ～C 6 Olefins and C of (2) 4 ～C 8 Is an ether of (a). The invention discovers that the preferable atmosphere can realize process coordination, is beneficial to further controlling the impurity phase of the components and is further beneficial to improving the electrochemical performance of the prepared material.
Preferably, the atmosphere containing volatile organic compounds also contains diluent gas;
preferably, the diluent gas is at least one of nitrogen and inert gas;
preferably, in the atmosphere containing volatile organic compounds, the volume content of the volatile organic compounds is more than or equal to 10%; preferably 10 to 30%.
According to the invention, under the innovation of the preparation of the precursor particles, the combined control of the roasting treatment and the temperature under the air source is further matched, so that the crystal phase purity, the crystal structure and the electrochemical performance of the prepared material can be further synergistically improved.
Preferably, the gas phase carbon deposition treatment time is 0.5-2 hours.
It is further preferred that the vapor deposition stage comprises a first heat treatment process at 200 to 250 ℃ and a second heat treatment process at 300 to 350 ℃. The time of the first section heat treatment process and the second section heat treatment process can be respectively 0.5-1 h.
The invention relates to a preparation method of a more specific uniform carbon-coated sodium ferrous fluorophosphate positive electrode active material, which comprises the following steps:
step (1): taking an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source as raw materials, dissolving the raw materials in an organic solvent or deionized water, and stirring to obtain a suspension A, wherein the solid content of the suspension is controlled to be 30% -60%;
step (2): transferring the suspension A into a ball mill, and ball milling to obtain a suspension B; wherein the granularity of the slurry after ball milling is D50 < 2 mu m, and the ball milling medium is preferably zirconia balls.
Step (3): transferring the suspension B into a sand mill, and performing sand milling to obtain a suspension C; wherein, the granularity of the slurry after sand grinding is D50 < 300nm, and the rotating speed of the sand grinder is preferably 1500-2400 rpm.
Step (4): spray drying the suspension C to obtain a spherical precursor; wherein the inlet temperature of spray drying is 180-270 ℃, and the spray rate is 20-40 ml/min.
Step (5): transferring the precursor into a closed aerated atmosphere furnace, and sintering to obtain carbon-coated sodium ferrous fluorophosphate; the sintering temperature in the step 5 is 550-600 ℃, and the heat preservation time is preferably 4-16 h.
Step (6): and (3) on the basis of the step (5), introducing a volatile organic gas source, and carrying out heat preservation treatment at 200-350 ℃ to obtain the uniform carbon-coated sodium ferrous fluorophosphate material.
The invention also provides a method for preparing the uniform carbon-coated ferrous sodium fluorophosphate material.
The invention also provides application of the carbon-coated ferrous sodium fluorophosphate material, which is used for preparing sodium ion batteries;
preferably used as a positive electrode active material for preparing sodium ion batteries.
The invention also provides a sodium ion battery anode material, which comprises the uniform carbon-coated sodium ferrous fluorophosphate anode material prepared at a low temperature.
Preferably, the positive electrode material further comprises a binder and a conductive agent. The binder and the conductive agent may be materials known in the industry, for example, the binder may be PVDF and the conductive agent may be acetylene black. The content of each component can also be adjusted based on the existing means, for example, the content of the binder is, for example, 5 to 15wt%; the content of the conductive agent is, for example, 5 to 15wt%, and the balance is the active material.
The invention also comprises a sodium ion battery anode, which comprises the carbon-coated sodium ferrous fluorophosphate anode material; preferably, the positive electrode comprises the carbon-coated sodium ferrous fluorophosphate positive electrode material.
The invention has the following remarkable characteristics:
aiming at the problems that carbon coating morphology, conductivity and product phase purity are difficult to take into account and electrochemical performance is not ideal in the carbon coating process of ferrous sodium fluorophosphate, the invention innovatively carries out spray drying-roasting or spray pyrolysis treatment on raw materials and organic carbon sources in advance, then carries out vapor deposition treatment in combination with further combined control of treatment processes, can realize synergy, can effectively control the heterogeneous problem of preparing ferrous sodium fluorophosphate by carbon coating, is beneficial to improving a carbon composite mode under mild conditions, improves graphitization degree and improves a conductive network, and can synergistically improve the electrochemical performance of the prepared material in a sodium ion battery.
The method has the advantages of low cost, large-scale production, environmental friendliness, simple operation and excellent industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of carbon-coated sodium ferrous fluorophosphate prepared in step (6) of example 1;
Detailed Description
Example 1
(1) Weighing 90.01Kg of ferric phosphate, 25.05Kg of sodium fluoride, 50.13Kg of sodium bicarbonate and 34.80Kg of glucose as iron sources, phosphorus sources, fluorine sources, sodium sources and organic carbon sources (namely, na: fe: P: F elements according to a stoichiometric molar ratio (Na: fe: P: F=2:1:1:1), dissolving the mixed materials in 200L of water, and stirring to obtain a suspension A, wherein the solid content of the suspension A is controlled to be 50%;
(2) Transferring the suspension A into a ball mill, rotating at 500rpm, ball milling for 5 hours, and controlling the particle size to D50 < 2 mu m to obtain a suspension B;
(3) Transferring the suspension B into a sand mill, rotating at 2000rpm, sand milling for 1h, and controlling the particle size to D50 < 300nm to obtain suspension C
(4) Spray drying the suspension C, controlling the inlet temperature to 200 ℃ and the flow to 35ml/min; obtaining a spherical precursor;
(5) Transferring the precursor into a rotary kiln, and calcining at 600 ℃ in nitrogen atmosphere for 10 hours to obtain carbon-coated sodium ferrous fluorophosphate (precursor particles);
(6) Then, introducing mixed gas of nitrogen and propylene as a heat treatment gas source, wherein the volume ratio is 9:1, and sintering for 1h at 320 ℃ (sintering temperature) to obtain uniform carbon-coated sodium ferrous fluorophosphate (XRD, see figure 1).
Example 2
The only difference compared to example 1 is that the glucose of step (1) is changed to an equal weight of citric acid, the other steps being unchanged. The roasting temperature in the step (5) is 550 ℃ and the time is 14h.
Example 3
The only difference compared to example 1 is that the iron phosphate of step (1) is exchanged for ferrous oxalate and monoammonium phosphate (wherein the molar amounts of Fe and P are the same as in example 1), the other steps being unchanged.
Example 4
The only difference compared to example 1 is that in step (4) the spray drying is changed to spray pyrolysis, the other steps being unchanged. For example, the spray pyrolysis temperature was 600 ℃, and the flow rate was the same as in example 1.
Example 5
The difference compared to example 1 is only that the sintering temperature in step (6) is 200℃and the time is 2 hours, the other steps being unchanged.
Example 6
The difference compared with example 1 is that in the mixed gas of nitrogen and propylene in the step (6), the volume ratio of nitrogen and propylene is 7:3, and other steps are unchanged.
Example 7
The only difference compared to example 1 is that the heat treatment gas source in step (6) is nitrogen-butyl ether: (butyl ether volume content 10%) and other steps are unchanged.
Example 8
The only difference compared to example 1 is that the heat treatment gas source in step (6) is nitrogen: propylene: mixed gas of butyl ether (volume ratio is 90:5:5), and other steps are unchanged.
Example 9
The difference compared with example 1 is only that in step (6), the first stage sintering is performed at 200℃for 0.5 hours in advance, followed by the second stage sintering at 320℃for 0.5 hours, the other steps being unchanged.
Comparative example 1
The difference compared to example 1 is only that the spray drying treatment of step (4) is not performed, but the drying treatment is performed using conventional oven drying, the other steps being unchanged.
Comparative example 2
The only difference compared to example 1 is that step (5) is sintered under a nitrogen atmosphere at 500 ℃ and the other steps are unchanged.
Comparative example 3
The only difference compared to example 1 is that step (5) is sintered under a nitrogen atmosphere at 700 ℃ and the other steps are unchanged.
Comparative example 4
The difference compared with example 1 is that propylene is not added to the heat treatment gas source in the step (6), but pure nitrogen is adopted, and other steps are unchanged.
Comparative example 5
The difference compared to example 1 is only that step (1) does not add an organic carbon source and the other steps are unchanged.
Comparative example 6
The only difference compared to example 1 is that the heat treatment of the gas phase organic matter of step (6) is not employed, but a conventional liquid phase post-compounding heat treatment carbon-coated process is employed, for example, the steps are as follows: the sodium ferrous fluorophosphate/C material prepared in the step (5) is mixed with glucose (the weight ratio of glucose to sodium ferrous fluorophosphate/C is 1:10) in solvent water through solid-phase ball milling, then is dried, and is calcined for 10 hours at 320 ℃ in nitrogen atmosphere.
Comparative example 7
The only difference compared to example 1 is that the sintering temperature in step (6) is 400℃and the other steps are unchanged.
The electrical properties of the sodium ferrous fluorophosphate prepared in each example and comparative example were tested:
the main testing steps are as follows:
(1) The battery shell with 2032 model is utilized, the positive electrode is a pole piece of the prepared sodium ferrous fluorophosphate, the current collector is aluminum foil, and the active substances (materials finally prepared in each example and comparative example) are as follows: conductive carbon (acetylene black): pvdf=7: 2:1, the negative electrode is sodium metal, and a fiber diaphragm (model Whatman Grade GF/D) is used for filling a battery, and the electrolyte is 1M NaClO4 (pure PC+5% FEC);
(2) Setting standing time to be 12h, setting a multiplying power charging program, setting multiplying power to be 1C, setting voltage interval to be 2.0V-4.0V, setting circulating temperature to be room temperature, and circulating for 1000 circles;
(3) The theoretical specific capacity of the sodium ferrous fluorophosphate is 124mAh/g;
the test results are shown in table 1:
it can be seen that by adopting the preparation process, the spray-roasting (or spray pyrolysis) -vapor deposition combined process, and the combined control of the sintering temperature and the vapor treatment temperature, the synergy can be realized unexpectedly, and better electrochemical performance can be obtained.
Claims (34)
1. A preparation method of a carbon-coated ferrous sodium fluorophosphate material is characterized in that raw material slurry containing an iron source, a phosphorus source, a fluorine source, a sodium source and an organic carbon source is subjected to spray drying-roasting treatment or spray pyrolysis treatment to obtain carbon composite precursor particles; the roasting temperature is 550-650 ℃; the temperature of spray pyrolysis is 550-650 ℃;
and then placing the precursor particles in an atmosphere containing volatile organic matters, and carrying out gas phase carbon deposition treatment at the temperature of 200-350 ℃ to obtain the carbon-coated ferrous sodium fluorophosphate material.
2. The method of preparing a carbon-coated ferrous sodium fluorophosphate material of claim 1, wherein the iron source is at least one of a phosphate and an organic acid salt of ferrous and/or ferric ions.
3. The method of making a carbon-coated ferrous sodium fluorophosphate material of claim 2 wherein the iron source is at least one of iron phosphate, ferrous oxalate dihydrate.
4. The method for preparing a carbon-coated ferrous sodium fluorophosphate material of claim 1, wherein the phosphorus source is at least one of phosphoric acid, ammonium phosphate, monoammonium phosphate, diammonium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and ferric phosphate.
5. The method for preparing a carbon-coated ferrous sodium fluorophosphate material as claimed in claim 1, wherein the fluorine source is at least one of sodium fluoride and ammonium fluoride.
6. The method for preparing a carbon-coated ferrous sodium fluorophosphate material of claim 1, wherein the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium organic acid salt, sodium oxide, sodium hydroxide.
7. The method for preparing a carbon-coated sodium ferrous fluorophosphate material as recited in claim 1, wherein the organic carbon source is a water-soluble organic substance.
8. The method of claim 7, wherein the organic carbon source is at least one of glucose, citric acid, starch, ascorbic acid, cyclodextrin, and polyethylene glycol.
9. The method of preparing a carbon-coated sodium ferrous fluorophosphate material of claim 1 wherein the solvent in the feedstock slurry comprises water.
10. The method for preparing a carbon-coated sodium ferrous fluorophosphate material as claimed in claim 1, wherein in the raw material slurry, na: fe: p: f has an element mole ratio of 1.9-2.1: 0.9 to 1.1:1:1.
11. the method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the weight ratio of the organic carbon source to the iron source is 1: 1-10.
12. The method for preparing a carbon-coated sodium ferrous fluorophosphate material as claimed in claim 1, wherein the solid particle size d50 in the raw material slurry is not more than 300 and nm.
13. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the solid content in the raw material slurry is 30-60 wt.%.
14. The method for preparing a carbon-coated sodium ferrous fluorophosphate material as recited in claim 1, wherein the raw material slurry is obtained by pulping the raw materials, ball milling and sand milling.
15. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the inlet temperature of the spray drying process is 180-270 ℃; the spraying rate is 20-40 ml/min.
16. The method for preparing a carbon-coated sodium ferrous fluorophosphate material of claim 1 wherein the roasting atmosphere is a protective atmosphere.
17. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the roasting temperature is 550-600 ℃.
18. The method for preparing the carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the heat preservation time at the roasting temperature is 4-16 hours.
19. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the particle size of the precursor material is 10-20 μm.
20. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the spray pyrolysis temperature is 550-600 ℃; the spraying rate is 20-40 ml/min.
21. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the volatile organic compound is an organic compound that is in a gaseous state at a temperature of 200-350 ℃.
22. The method for preparing a carbon-coated sodium ferrous fluorophosphate material as recited in claim 21, wherein said volatile organic compound is C 1 ~C 6 Alkane, C 2 ~C 6 Olefins, C 2 ~C 6 Alkyne, C 4 ~C 10 At least one of the ethers of (a).
23. The method of claim 22, wherein the volatile organic compound comprises C 2 ~C 6 Olefins and C of (2) 4 ~C 8 Is an ether of (a).
24. The method for preparing a carbon-coated sodium ferrous fluorophosphate material as recited in claim 1, wherein said atmosphere containing volatile organic compounds further contains a diluent gas.
25. The method for preparing a carbon-coated sodium ferrous fluorophosphate material of claim 24, wherein the diluent gas is at least one of nitrogen and inert gas.
26. The method of claim 24, wherein the volatile organic compound is present in the atmosphere in an amount greater than or equal to 10% by volume.
27. The method for preparing a carbon-coated sodium ferrous fluorophosphate material of claim 26, wherein the volume content of volatile organic compounds in the atmosphere containing volatile organic compounds is 10-30%.
28. The method for preparing a carbon-coated sodium ferrous fluorophosphate material according to claim 1, wherein the vapor deposition stage comprises a first heat treatment process at 200-250 ℃ and a second heat treatment process at 300-350 ℃.
29. A carbon-coated sodium ferrous fluorophosphate material prepared by the method of any one of claims 1-28.
30. Use of a carbon-coated ferrous sodium fluorophosphate material as claimed in claim 29 as a positive electrode active material for a sodium ion battery.
31. The use of a carbon-coated sodium ferrous fluorophosphate material as claimed in claim 30 as a positive electrode active material for the preparation of sodium ion batteries.
32. The use of a carbon-coated sodium ferrous fluorophosphate material as claimed in claim 31 as a positive electrode active material for the preparation of a positive electrode of a sodium ion battery.
33. A sodium ion battery comprising the carbon-coated ferrous sodium fluorophosphate material of any one of claims 30-32.
34. A sodium ion battery as defined in claim 33, wherein said carbon coated ferrous sodium fluorophosphate material is included in the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210440489.9A CN114914413B (en) | 2022-04-25 | 2022-04-25 | Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210440489.9A CN114914413B (en) | 2022-04-25 | 2022-04-25 | Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114914413A CN114914413A (en) | 2022-08-16 |
| CN114914413B true CN114914413B (en) | 2024-03-26 |
Family
ID=82765257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210440489.9A Active CN114914413B (en) | 2022-04-25 | 2022-04-25 | Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114914413B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115863573A (en) * | 2022-12-05 | 2023-03-28 | 南京航空航天大学 | Composite positive electrode material for sodium ion battery and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306772A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Method for preparing fluorine sodium ferrous phosphate positive electrode material of mixed ion battery |
| CN105428649A (en) * | 2015-12-09 | 2016-03-23 | 天津大学 | Nano-carbon coated sodium ferrous fluorophosphates and preparation method of hydrothermal method |
| CN105810902A (en) * | 2016-03-11 | 2016-07-27 | 天津大学 | Method for preparing nanocarbon-clad Na2FePO4F by through solvothermal |
| CN106229505A (en) * | 2016-08-17 | 2016-12-14 | 深圳市贝特瑞纳米科技有限公司 | A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it |
| CN106784696A (en) * | 2016-12-26 | 2017-05-31 | 深圳市贝特瑞纳米科技有限公司 | A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use |
| CN107658438A (en) * | 2017-08-29 | 2018-02-02 | 天津大学 | Prepare fluorophosphoric acid Naferon porous spongy structural material and method |
| CN109037659A (en) * | 2018-09-04 | 2018-12-18 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material |
| CN109244462A (en) * | 2018-11-20 | 2019-01-18 | 浙江瑞邦科技有限公司 | A kind of preparation method of high conductivity LiFePO 4 material |
| CN114122311A (en) * | 2021-11-26 | 2022-03-01 | 中南大学 | Carbon-coated sodium ferrous fluorophosphate cathode active material, preparation thereof and application thereof in sodium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5850006B2 (en) * | 2013-08-12 | 2016-02-03 | トヨタ自動車株式会社 | Negative electrode active material for sodium ion battery, sodium ion battery, and method for producing negative electrode active material for sodium ion battery |
-
2022
- 2022-04-25 CN CN202210440489.9A patent/CN114914413B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306772A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Method for preparing fluorine sodium ferrous phosphate positive electrode material of mixed ion battery |
| CN105428649A (en) * | 2015-12-09 | 2016-03-23 | 天津大学 | Nano-carbon coated sodium ferrous fluorophosphates and preparation method of hydrothermal method |
| CN105810902A (en) * | 2016-03-11 | 2016-07-27 | 天津大学 | Method for preparing nanocarbon-clad Na2FePO4F by through solvothermal |
| CN106229505A (en) * | 2016-08-17 | 2016-12-14 | 深圳市贝特瑞纳米科技有限公司 | A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it |
| CN106784696A (en) * | 2016-12-26 | 2017-05-31 | 深圳市贝特瑞纳米科技有限公司 | A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use |
| CN107658438A (en) * | 2017-08-29 | 2018-02-02 | 天津大学 | Prepare fluorophosphoric acid Naferon porous spongy structural material and method |
| CN109037659A (en) * | 2018-09-04 | 2018-12-18 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material |
| CN109244462A (en) * | 2018-11-20 | 2019-01-18 | 浙江瑞邦科技有限公司 | A kind of preparation method of high conductivity LiFePO 4 material |
| CN114122311A (en) * | 2021-11-26 | 2022-03-01 | 中南大学 | Carbon-coated sodium ferrous fluorophosphate cathode active material, preparation thereof and application thereof in sodium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| Carbon coated hollow Na2FePO4F spheres for Na-ion battery cathodes;Alex Langrock等;《Journal of Power Sources》;第第223卷卷;第62-67页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114914413A (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Dual-carbon enhanced silicon-based composite as superior anode material for lithium ion batteries | |
| CN109244391B (en) | Nitrogen-doped carbon-coated lithium manganese iron phosphate material and preparation method thereof | |
| CN102522546B (en) | Method for preparing lithium iron phosphate serving as cathode material of nano-level lithium ion battery | |
| CN112768673A (en) | Na4Fe3-x(PO4)2P2O7Positive electrode material of/C sodium ion battery and preparation method and application thereof | |
| CN110299528B (en) | Fluorinated phosphate ferric sodium pyrophosphate @ C @ RGO composite material, preparation method thereof and application thereof in sodium ion battery | |
| CN109103433B (en) | Nitrogen-doped carbon-coated lithium iron phosphate composite material and preparation method thereof | |
| CN114122311B (en) | Carbon-coated ferrous sodium fluorophosphate active material, preparation method thereof and application thereof in sodium electricity | |
| CN1911792A (en) | Microwave synthesis method for carbon coated iron phosphate of ion battery composite anode material | |
| CN103165896A (en) | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| CN102097616A (en) | Preparation method of high-energy and high-power density nano-scale lithium iron phosphate powder | |
| CN114665058A (en) | Preparation method of lithium ion battery anode material lithium iron manganese phosphate | |
| CN104577123A (en) | Preparation method of cathode material for lithium ion cell | |
| CN102403505A (en) | Method for preparing lithium ion battery cathode material in-situ carbon coated lithium manganese borate composite material | |
| CN114914413B (en) | Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery | |
| CN116487545A (en) | Carbon composite ferric sodium pyrophosphate composite material, preparation method thereof and application thereof in sodium ion battery | |
| Zhang et al. | Novel synthesis of LiMnPO4· Li3V2 (PO4) 3/C composite cathode material | |
| CN103441278A (en) | Method for preparing carbon-coated lithium iron phosphate through microwave pyrolysis of ionic liquid | |
| CN103159201B (en) | A kind of high pressure, low temperature method preparing carbon-coated LiFePO 4 for lithium ion batteries anode composite material of lithium ion battery | |
| CN114005974A (en) | Silica anode material, preparation method of silica anode material and lithium ion battery | |
| CN111900366B (en) | SiO containing lithium x Method for preparing powder | |
| CN105084338A (en) | Method for preparing anode material lithium ion cell lithium iron phosphate | |
| CN103840159A (en) | Synthesizing method for lithium ion anode material LiFePO4/C | |
| CN114976020B (en) | Modified lithium iron phosphate, preparation method thereof and lithium ion battery | |
| CN116534830A (en) | Sodium ion battery positive electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230531 Address after: No. 108 Jinzhou Avenue, Ningxiang High tech Industrial Park, Changsha City, Hunan Province, 410604 Applicant after: Hunan Nabang New Energy Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Applicant before: CENTRAL SOUTH University |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |